KR101411529B1 - Primerless type polyurethane sealant composition for adhering to paint of vehicle - Google Patents

Abstract

(A) a compound (a) containing two or more isocyanate groups in the presence of a plasticizer (d) is reacted with a polyol (b) having two or three hydroxyl groups to prepare a polyurethane sealant composition having a molecular weight of 10,000 A silane-modified polyurethane prepolymer prepared by the addition reaction of a silane compound having 1 to 2 active hydrogens on the urethane prepolymer without a catalyst under a heat source; And (B) a reactive silicone oligomer. The polyurethane sealant composition according to the present invention does not require a primer when adhering to a clear paint for automobiles based on an automobile paint, especially a silicone-modified acrylic resin, has excellent storability, and has an excellent adhesion on application under severe conditions .

Description

TECHNICAL FIELD [0001] The present invention relates to a polyurethane sealant composition which does not require a primer when bonding an automotive paint,

The present invention relates to a polyurethane sealant composition which does not require a primer when bonding an automotive coating material, and more particularly to a polyurethane sealant composition which is excellent in the storage stability of a final silane-modified polyurethane prepolymer by using a heat source instead of a catalyst affecting storability in the production of a urethane prepolymer And a reactive silicone oligomer is added to improve reaction bonding with the silane present in automotive clear coatings, thereby eliminating the need for a primer.

[0002] Polyurethane sealants are widely used as urethane adhesives used in automobile windshields, rear windows and the like without bolting, and usually contain at least one urethane prepolymer.

U.S. Patent No. 2006/0270807 A1 discloses a process for producing a urethane sealant for an automobile glass fastener having good adhesion without the use of a vehicle primer by modifying an urethane prepolymer at the end with an isocyanate residue remaining at the end and aminosilane or mercaptosilane have. In this patent, although the reaction time was shortened by using a catalyst in the production of the urethane prepolymer, the urethane prepolymer was poor in storage stability, and the clearance for automobile paint ((GENI CLEAR, DUPONT) having a silicone- And the adhesion (knife cut adhesion) of the urethane sealant was poor when the conditions (baking conditions of the paint specimen at low temperature and low humidity, etc.) were observed.

In addition, in International Patent Application No. PCT / US2006 / 020938, a urethane prepolymer is prepared in the presence of a catalyst, an isocyanate-reactive silane and a polyisocyanate adduct are added, a tertiary amine and an organometallic compound are added, A urethane sealant composition was prepared. However, when the urethane sealant is applied under a relatively severe condition, there is a disadvantage that the adhesion is poor.

It is an object of the present invention to solve the above-mentioned problems, and it is an object of the present invention to provide a clear paint for automobiles based on automobile paints, in particular silicone modified acrylic resins, which does not require a primer and has excellent storability, And to provide an excellent polyurethane sealant composition.

The automotive clear paint containing a silicone-modified acrylic resin shows alkoxysilane on the clear surface after baking, and thus shows poor adhesion to polyurethane sealant when the polyurethane sealant having only an isocyanate residue is used. In particular, it shows poor adhesion after baking under low temperature / low humidity. This is because alkoxysilane which is not changed into alkoxysilanol is present on the clear surface more and deteriorates the adhesion. In order to overcome this problem, the polyurethane sealant composition according to the present invention is improved in adhesion by using a polyurethane prepolymer modified with a silane group capable of bonding to the alkoxysilane on the clear surface and to improve adhesion in harsh conditions And a reactive silicone oligomer containing a large amount of a silane group is added as an additive.

Specifically, the polyurethane sealant composition which does not require the primer according to the present invention is characterized by comprising (A) a compound (a) containing two or more isocyanate groups in the presence of the plasticizer (d) and a polyol having two or three hydroxyl groups ) To prepare a urethane prepolymer having a molecular weight of 10,000 to 20,000 and then subjecting the urethane prepolymer to a silane-modified polyurethane preparation (c) having an active hydrogen-containing silane compound polymer; And (B) a reactive silicone oligomer.

Preferably, based on the total weight of the polyurethane sealant composition, 50 to 70% by weight of the silane-modified polyurethane prepolymer; From 0.5 to 1% by weight of reactive silicone oligomers and from 29 to 49% by weight of other additives.

Preferably, the silane-modified polyurethane prepolymer comprises 10 to 20% by weight, based on the total weight of the silane-modified polyurethane prepolymer, of a compound (a) comprising two or more isocyanate groups; 40 to 80% by weight of a polyol (b) having 2 or 3 hydroxyl groups; 1 to 10% by weight of a silane compound (c) having 1 to 2 active hydrogen atoms; And 5 to 48% by weight of a plasticizer (d).

Preferably, the compound (a) containing two or more isocyanate groups is selected from the group consisting of diphenylmethane diisocyanate, isophorone diisocyanate, bis (4-isocyanatocyclohexyl) methane, trimethylene diisocyanate, tetramethylene diisocyanate, Isocyanate, isocyanate, hexamethylene diisocyanate, propylene diisocyanate, ethylene diisocyanate, 2,3-dimethylethylene diisocyanate, 1-methyltrimethylene diisocyanate, 1,3-cyclopentene diisocyanate, 1,2-cyclopentene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6- toluene diisocyanate and 5-isocyanato- A group consisting of 1- (isocyanatomethyl) -1,3,3-trimethyl-cyclohexane It may be selected from.

Preferably, the polyol (b) having two or three hydroxy groups can be selected from polyester polyols, polyether polyols, poly (alkylene carbonate) polyols and mixtures thereof, A polypropylene glycol having two hydroxy groups having a molecular weight of 3,000 to 3,000 and a polypropylene triol having three hydroxy groups having a molecular weight of 3,000 to 6,000. At this time, polypropylene glycol and polypropylene triol are preferably mixed at a weight ratio of 40:60.

Preferably, the heat source is provided in a temperature range of 70 to 90 占 폚.

Preferably, the silane compound (c) having 1 to 2 active hydrogens is N, N'-bis ((3-trimethoxysilyl) propyl) amine.

Preferably, (B) the reactive silicone oligomer may be represented by the formula:

In the above formulas, n is 1 or 2, 1 is 2 to 4, m is 1 or 2, R is an alicyclic hydrocarbon having 3 to 6 carbon atoms, benzene, an aliphatic hydrocarbon having 2 to 11 carbon atoms, and R ' An alkyl group having 2 to 6 carbon atoms, and BL is selected from phenols, imidazoles, pyrazoles, oximes, alcohols and acetates as a blocking agent reacting with NCO.

Hereinafter, the present invention will be described in more detail.

A polyurethane sealant composition which does not require a primer according to the present invention is characterized by comprising (A) a silane-modified polyurethane prepolymer and (B) a reactive silicone oligomer.

(A) a silane-modified polyurethane prepolymer

The silane-modified polyurethane prepolymer according to the present invention is produced by reacting a compound (a) containing two or more isocyanate groups with a polyol (b) having two or three hydroxy groups in the presence of a plasticizer (d) (C) having 1 to 2 active hydrogens on the urethane prepolymer without a catalyst under a heat source after the preparation of the prepolymer.

The compound (a) comprising two or more isocyanate groups used in the preparation of the silane-modified polyurethane prepolymer of the present invention includes any aliphatic, alicyclic, araliphatic, heterocyclic or aromatic isocyanate or a mixture thereof. Preferred is at least one of diphenylmethane diisocyanate, isophorone diisocyanate, bis (4-isocyanatocyclohexyl) methane, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, propylene diisocyanate, 1,3-cyclopentene diisocyanate, 1,2-cyclopentene diisocyanate, 1,3-cyclohexene diisocyanate, 1,3-cyclohexene diisocyanate, Phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate and 5-isocyanato-1- (isocyanatomethyl) -1,3 , 3-trimethyl-cyclohexane, and more preferably diphenylmethane An isocyanate.

The polyol (b) having two or three hydroxyl groups used in preparing the silane-modified polyurethane prepolymer of the present invention may be selected from polyester polyols, polyether polyols, poly (alkylene carbonate) polyols and mixtures thereof have. Polyester polyols, polyether polyols, poly (alkylene carbonate) polyols are well known in the art. In a specific embodiment of the present invention, a mixture of polypropylene glycol having two hydroxy groups having a molecular weight of 1,000 to 3,000 and polypropylene triol having three hydroxy groups having a molecular weight of 3,000 to 6,000 can be used.

The silane compound (c) having 1 to 2 active hydrogen atoms used in the preparation of the silane-modified polyurethane prepolymer of the present invention is an addition product to a urethane prepolymer prepared by reacting a polyol with a compound containing an isocyanate group . The silane compound (c) having one to two active hydrogens may be a silane compound having an active hydrogen reactive with an isocyanate group, such as mercaptosilane or aminosilane, mercaptotrialkoxysilane, or aminotrialkoxysilane. It is not. In a particular embodiment of the present invention, N, N'-bis ((3-trimethoxysilyl) propyl) amine can be used.

Diisodecyl phthalate (DIDP), dioctyl phthalate (DOP), dibutyl phthalate (DBP) and the like may be used as the plasticizer (d) used in the production of the silane-modified polyurethane prepolymer of the present invention, but the present invention is not limited thereto. In a particular embodiment of the present invention, the plasticizer is diisodecyl phthalate.

The heat source according to the invention provides a temperature range of 70 to 90 캜, preferably 80 캜. The present invention is characterized in that the addition reaction is carried out without a catalyst by the provided heat source, and thus the storage stability of the silane-modified polyurethane prepolymer can be improved by carrying out the addition reaction without catalyst.

Preferably, the silane-modified polyurethane prepolymer comprises 10 to 20% by weight, based on the total weight of the silane-modified polyurethane prepolymer, of a compound (a) comprising two or more isocyanate groups; 40 to 80% by weight of a polyol (b) having 2 or 3 hydroxyl groups; 1 to 10% by weight of a silane compound (c) having 1 to 2 active hydrogen atoms; And 5 to 48% by weight of a plasticizer (d). It is possible to provide excellent shelf life within the above content range.

The silane-modified polyurethane prepolymer of the present invention has a viscosity of about 90 to 120 PS, an NCO% of about 1.4 to 1.5, and a weight average molecular weight of about 10,000 to 20,000.

In the polyurethane sealant composition according to the present invention, the silane-modified polyurethane prepolymer is preferably used in an amount of 50 to 70% by weight based on the total weight of the polyurethane sealant composition. There is an effect that the adhesion is good within the above range.

(B) a reactive silicone oligomer

The reactive silicone oligomer according to the present invention is prepared by reacting a compound having two isocyanate groups with a blocking agent in an amount equivalent to only one equivalent, and the remainder is a prepolymer prepared by reacting a monomer having 2 to 3 hydroxy groups in a monomer ratio or a molar ratio Is a compound prepared by reacting an alkyltrialkoxysilane in a prepolymer, hydrolyzing the remaining hydroxy group, and further hydrolyzing alkyltrialkoxysilane with water (ionized water).

Preferably 10 to 20% by weight, based on the total weight of the reactive silicone oligomer, of a compound having two isocyanate groups; 5 to 25% by weight of a blocking agent; 5 to 20% by weight of a monomer having 2 to 3 hydroxyl groups, 30 to 60% by weight of an alkyltrialkoxysilane; As the chain extender, 1 to 10% by weight of ionized water; And 0.01 to 0.5% by weight of a catalyst.

According to one embodiment of the present invention, the compound having two isocyanate groups is preferably hexamethyl diisocyanate, the blocker is preferably dimethylpyrazole, and the monomer having two or three hydroxyl groups is preferably trimethylolpropane It is preferable to use methyltrimethoxysilane as the alkyltrialkoxysilane, and the catalyst may be prepared by using phenyl acid phosphate such as monophenyl acid phosphate or diphenyl acid phosphate (phosphoric acid diphenyl ester) .

The reactive silicone oligomers according to the present invention can be represented by the formula:

N is 1 or 2, 1 is 2 to 4, m is 1 or 2, R is an alicyclic hydrocarbon having 3 to 6 carbon atoms, benzene, an aliphatic hydrocarbon having 2 to 11 carbon atoms, and R ' An alkyl group having 2 to 6 carbon atoms, and BL is selected from phenols, imidazoles, pyrazoles, oximes, alcohols and acetates as a blocking agent reacting with NCO.

Preferably, n is 1 or 2, l is 2 or 3, m is 1, R is hexyl, R 'is ethyl, propyl, butyl, pentyl or hexyl and BL is 3,5- boil down.

Preferably, the reactive silicone oligomer according to the present invention is a block isocyanate-modified alkyl silane.

In the polyurethane sealant composition according to the present invention, the reactive silicone oligomer is preferably used in an amount of 0.5 to 1% by weight based on the total weight of the polyurethane sealant composition. There is an effect that the adhesion is good within the above range.

(C) Other additives

The polyurethane sealant composition which does not require a primer according to the present invention can be used as an adhesion promoter, a pigment, a plasticizer, a catalyst (curing accelerator), a leveling agent, a wetting agent, a flow control agent, A viscosity modifier, a dye, an ultraviolet absorber, a heat stabilizer, an antioxidant, and a mixture thereof. The amount of the additive may be 29 to 49% by weight based on the total weight of the polyurethane sealant composition. The amount of the additive may be suitably adjusted by a person skilled in the art depending on the type and use of the additive, and is not particularly limited .

Adhesion-promoting agents that can be used in the present invention serve to assist adhesion enhancement of reactive silicone oligomers, including, but not limited to, isocyanate resins. In a particular embodiment of the invention, a mixture of Desmor N-3300 from Bayer and Dyuranate 24A-100 from Asahi Kasei can be used.

Pigments that may be used in the present invention include, but are not limited to, carbon black, titanium dioxide, calcium carbonate, iron oxide, aluminum trihydroxide, mica, calcium metasilicate and mixtures thereof. In a particular embodiment of the present invention, the pigment is a mixture of carbon black and calcium carbonate.

Diisodecyl phthalate (DIDP), dioctyl phthalate (DOP), dibutyl phthalate (DBP) and the like can be used as the plasticizer that can be used in the present invention, but the present invention is not limited thereto. In a particular embodiment of the present invention, the plasticizer is diisodecyl phthalate.

The catalyst (curing accelerator) that can be used in the present invention is one for accelerating curing, and includes tin compounds, amine compounds and the like, such as dibutyl tin dilaurate, dimethyl tin dilaurate, dibutyl tin diacetate, tin octylate, (2-dimethylaminoethyl) ether, triethylenediamine, pentamethyldiethylenetriamine, N, N'-dibutyl tin oxide, dimorpholinodialkyl ether wherein the number of carbon atoms of the alkyl group is from 1 to 4, , N-dimethylcyclohexylamine, or a mixture thereof may be used, but the present invention is not limited thereto. In a particular embodiment of the invention, the catalyst may be a mixture of dioctyltin dilaurate and dimorpholonodiethyl ether.

The chrysanthemum suppositories that may be used in the present invention may include, but are not limited to, Aerosil, C-818, or mixtures thereof. In a particular embodiment of the present invention, the mixture of C-818 and Aerosil can be used as the herbicide.

The viscosity controlling agent that can be used in the present invention may be appropriately selected from known materials and is not particularly limited. In a particular embodiment of the present invention, the viscosity modifier may be xylene.

The polyurethane sealant composition according to the present invention does not require a primer when adhering to a clear paint for automobiles based on an automobile paint, especially a silicone-modified acrylic resin, has excellent storability, and has an excellent adhesion on application under severe conditions .

Hereinafter, the present invention will be described in detail with reference to examples and comparative examples. However, the examples are for illustrative purposes only and are not intended to limit the scope of the present invention.

Production Example 1: Preparation of urethane prepolymer

A separable flask was charged with 300 g of diisodecyl phthalate, 220 g of polypropylene glycol having a molecular weight of about 1,000 and a hydroxyl number of 2, a polypropylene trioleate having a molecular weight of about 5,000 and a hydroxyl number of 3 and a stirrer, condenser, thermometer, 300 g of this product were introduced. 100 g of diphenylmethane diisocyanate sufficiently dissolved under nitrogen substitution was introduced and the temperature was raised to 80 DEG C without a catalyst to react. The viscosity of the prepared urethane prepolymer is 90PS, the NCO% is 1.7, and the weight average molecular weight is 15,000.

Preparation Example 2: Preparation of silane-modified polyurethane prepolymer

The urethane prepolymer prepared in Preparation Example 1 was heated to 80 ° C without a catalyst and 14 g of N, N'-bis ((3-trimethoxysilyl) propyl) amine was introduced therein. Respectively. The prepared silane-modified polyurethane prepolymer had a viscosity of 105 PS, an NCO% of 1.45 and a weight average molecular weight of 17,000.

Next, the same raw materials as those of the silane-modified polyurethane prepolymer prepared in Production Example 2 were used, and the physical properties of the urethane prepolymer (Comparative Example 1) prepared using 0.5 g of tin catalyst in the production of the urethane prepolymer were compared and shown in Table 1 .

Production Example 2 Comparative Example  One 60 ° C 80 ℃ 60 ° C 80 ℃ Viscosity increase rate (%) 153% increase 168% increase 230% increase 270% increase NCO% reduction rate (%) 10% reduction 11% reduction 32% reduction 48% reduction

As can be seen from Table 1, it was confirmed that the silane-modified polyurethane prepolymer of Preparation Example 2 according to the present invention had better storability in accordance with the temperature change than the urethane prepolymer of Comparative Example 1 prepared using the catalyst have.

Production Example 3: Preparation of reactive silicone oligomer

A separable flask was equipped with a stirrer, condenser, thermometer and nitrogen pipe, and 110 g of butyl acetate and 108 g of dimethylpyrazole were introduced. 120 g of hexamethyl diisocyanate was slowly added thereto while maintaining the temperature at 45 캜 or lower while feeding nitrogen gas and stirring at a low speed. When the filling was completed, the temperature was maintained at 45 ° C for 1 hour, the temperature was raised to 80 ° C, and 155 g of trimethylolpropane was introduced at 80 ° C. Thereafter, when the NCO% dropped to 0.03% or less, it was cooled to 70 ° C or lower. After cooling, 315 g of methyltrimethoxysilane was added, and 0.3 g of phosphoric acid diphenyl ester was continuously added, and the mixture was refluxed for 1 hour. Thereafter, 283 g of methyltrimethoxysilane and 79 g of ionized water were added in this order, and the mixture was maintained at reflux for 4 hours. In order to remove methanol generated by the reaction, normal pressure was recovered. Finally, 35 g of trimethylolpropane, Acetate was added and the final solid content was measured. The solid content was adjusted to 70 ± 2% with butyl acetate to prepare a reactive silicone oligomer.

Example 1: Preparation of polyurethane sealant composition

20 g of the silane-modified polyurethane prepolymer prepared in Preparation Example 2, 20 g of diisodecyl phthalate, 20 g of Desmor N-3300, 20 g of Dylanate 24A-100, 20 g of xylene, 5 g of the silicone oligomer were stirred in a Planetary mixer under vacuum at a speed of 30 for 30 minutes. After the stirring was stopped and the vacuum was removed by using nitrogen, 230 g of carbon black, 63 g of calcium carbonate and 1.5 g of aerosol were put into the mixture and stirred at a speed of 40 for 1 hour. After stirring was stopped and the vacuum was removed with nitrogen, the mixture was added with 12.5 g of chiral additive (C-818 supplied by YRC), 10 g of xylene, 0.23 g of neostann U-810 (supplied by Nitto Kasei) 1.2 g) was added thereto and stirred at a speed of 30 for 15 minutes to prepare a polyurethane sealant composition.

Comparative Examples 2 to 4: Preparation of polyurethane sealant composition

The composition shown in Table 2 was carried out in the same manner as in Example 1 to prepare a polyurethane sealant composition.

Component (% by weight) Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 The polymer of Preparation Example 1 - 600 600 The polymer of Preparation Example 2 60.0 60.0 - - The reactive silicone oligomer of Preparation Example 3 0.5 - 5 - Diisodecyl phthalate 2.0 2.0 20 20 Xylene 2.0 2.0 20 20 N-3300 2.0 2.0 20 20 24A-100 2.0 2.0 20 20 Carbon black 23.0 23.0 230 230 Calcium carbonate 6.3 6.3 63 63 Aerosil 0.15 0.15 0.15 0.15 C-818 (chimney additive) 0.13 0.13 0.13 0.13 Dioctyl tin dilaurate (U-810) 0.023 0.023 0.023 0.023 Xylene 1.0 1.0 1.0 1.0 Dimorpholonodiethyl ether (DMDEE) 0.897 0.897 0.897 0.897 Sum 100.0 100.0 100.0 100.0 Low temperature / low humidity adhesion 100% C / F 80% C / F 0% C / F 0% C / F ㅇ Low temperature / low humidity baking condition: 5 ℃ × 35% RH
ㅇ Terminology interpretation: C / F (cohesive failure of adhesive layer)

Test Example 1: Low temperature / low humidity adhesion property

In the environmental chamber where temperature and humidity can be adjusted, Baking specimens were tested according to MS-715-25 of Hyundai / Kia automobile standard. After applying the compositions of Examples 1 to 2, 3 and 4 to the prepared specimens, the specimens were allowed to stand at 20 ° C and 65% RH for 7 days, and then subjected to a knife cut adhesion test (room temperature adhering property) The samples were immersed in the same specimen at 20 ° C × 65% RH for 3 days, immersed in water at 40 ° C for 14 days, and then subjected to a knife cut adhesion test (waterproof adhesion) After being left for 3 days at 20 ° C and 65% RH, the sample was immersed for 14 days in a solution of 1/1 ratio of window washer solution and distilled water. After that, the knife cut adhesion test was carried out. , Left standing at 20 ° C × 65% RH for 3 days, left at 90 ° C for 3 hours, left at -30 ° C for 3 hours, left at 40 ° C × 90% for 15 hours, followed by 10 cycles The knife cut adhesion test (heat cycle adhesion) was conducted at 20 ° C × 65% RH for 3 days After leaving for 1,000 hours in a Sunshine Weather-O-Meter, the knife cut adhesion test was performed (weather-resistant adhesion).

Temperature / humidity conditions Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 5 ° C, 25% RH 100% C / F 80% C / F 0% C / F 0% C / F 5 ° C, 35% RH 100% C / F 80% C / F 0% C / F 0% C / F 5 ° C, 45% RH 100% C / F 80% C / F 0% C / F 0% C / F 5 ° C, 55% RH 100% C / F 90% C / F 0% C / F 0% C / F 5 ° C, 65% RH 100% C / F 90% C / F 0% C / F 0% C / F 5 ℃, 75% RH 100% C / F 90% C / F 0% C / F 0% C / F ㅇ Adhesiveness measurement method: Knife cut adhesion
Temperature / Humidity Conditions: DUPONT GEN IV CLEAR Baking S / C
Normal temperature / Domestic water / Heat resistance / Chemical resistance / Heat cycle / Weather resistance

From Table 3, it was confirmed that the silicone-modified urethane resin was used as a substrate and the silicone-modified oligomer as the adhesion promoter was used in Example 1 as a result of adhesion at low temperature / low humidity adhesion. This means that the silicon-modified resin and the silicon-modified oligomer can overcome the adhesion after low-temperature / low-humidity baking which is difficult to overcome with the prior art (urethane resin).

Claims (10)

(A) reacting a compound (a) containing two or more isocyanate groups in the presence of a plasticizer (d) with a polyol (b) having two or three hydroxy groups to prepare a urethane prepolymer having a molecular weight of 10,000 to 20,000, A silane-modified polyurethane prepolymer prepared by the addition reaction of a silane compound (c) having 1 to 2 active hydrogens to the urethane prepolymer without a catalyst under a catalyst; And
(B) a reactive silicone oligomer. The method according to claim 1,
Based on the total weight of the polyurethane sealant composition,
50 to 70% by weight of silane-modified polyurethane prepolymer;
0.5 to 1% by weight of a reactive silicone oligomer; And
And 29 to 49 wt% of other additives,
The other additives may be selected from the group consisting of an adhesion promoting agent, a pigment, a plasticizer, a curing accelerator, a leveling agent, a wetting agent, a flow control agent, an anti-filming agent, a chelating agent, a defoaming agent, a filler, an adhesion promoter, An antioxidant, and a mixture thereof. Polyurethane sealant composition. The method according to claim 1,
The silane-modified polyurethane prepolymer, based on total weight,
10 to 20% by weight of a compound (a) containing two or more isocyanate groups;
40 to 80% by weight of a polyol (b) having 2 or 3 hydroxyl groups;
1 to 10% by weight of a silane compound (c) having 1 to 2 active hydrogen atoms; And
And 5 to 48% by weight of a plasticizer (d). The method according to claim 1,
The compound (a) containing two or more isocyanate groups is a compound
Diphenylmethane diisocyanate, isophorone diisocyanate, bis (4-isocyanatocyclohexyl) methane, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, propylene diisocyanate, ethylene diisocyanate, 2 , 3-dimethylethylene diisocyanate, 1-methyltrimethylene diisocyanate, 1,3-cyclopentene diisocyanate, 1,4-cyclopentene diisocyanate, 1,2-cyclopentene diisocyanate, Isocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate and 5-isocyanato-1- (isocyanatomethyl) ≪ RTI ID = 0.0 > trimethyl-cyclohexane. ≪ / RTI > The method according to claim 1,
The polyol (b) having 2 or 3 hydroxy groups is,
A polyester polyol, a polyether polyol, a poly (alkylene carbonate) polyol, and mixtures thereof. The method according to claim 1,
The polyol (b) having 2 or 3 hydroxy groups is,
Is a mixture of a polypropylene glycol having two hydroxy groups having a molecular weight of 1000 to 3000 and a polypropylene triol having three hydroxy groups having a molecular weight of 3,000 to 6,000. The method according to claim 1,
Wherein the heat source is provided in a temperature range of 70 to 90 占 폚. The method according to claim 1,
Wherein the silane compound (c) having 1 to 2 active hydrogens is N, N'-bis ((3-trimethoxysilyl) propyl) amine. The method according to claim 1,
(B) a reactive silicone oligomer is represented by the following formula:

In this formula,
n is 1 or 2, l is 2 to 4, m is 1 or 2,
R is an alicyclic hydrocarbon having 3 to 6 carbon atoms, benzene, an aliphatic hydrocarbon having 2 to 11 carbon atoms,
R 'is an alkyl group having 2 to 6 carbon atoms,
BL is selected from phenols, imidazoles, pyrazoles, oximes, alcohols and acetates as blocking agents which react with NCO. The method according to claim 1,
The reactive silicone oligomer (B)
10 to 20% by weight, based on the total weight of the reactive silicone oligomer, of a compound having two isocyanate groups; 5 to 25% by weight of a blocking agent; 5 to 20% by weight of a monomer having 2 to 3 hydroxyl groups, 30 to 60% by weight of an alkyltrialkoxysilane; As the chain extender, 1 to 10% by weight of ionized water; And 0.01 to 0.5% by weight of a catalyst.